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By Jose M. Sobral

The approximate production of petroleum in the various fields and for the country as a whole is shown in the following table, the figures for the later months of the year being estimated. Among the developments of the year may be mentioned the finding by the Standard Oil Co. of a small production, about 6290 bbl., at Aguas Blancas in the Province of Salta near the Bolivian border, and of about 88,000 bbl. at Lomitas, near Tartagal in the same province. The Government (Yaciementos Petroliferos Fiscales) in the last four months of the year also obtained about 6290 bbl, from Quebrada Galarce. .The oil found in Salta is of good grade and while the quantity is small great hopes of larger production are entertained. Approximate Total Argentine Production for 1928 Barrels Barrels Comodoro Rivadavia............................... 8,165,615 Plaza Huincul..................................... 783,514 8,949,129 Distribution of Production Government, Comodoro Rivadavia................... 5,165,159 Government, Plaza Huincul......................... 306,166 5,471,325 Private, Comodoro Rivadavia....................... 3,000,456" Private, Plaza Huincul............................. 477,348b 3,477,804 a The companies represented are Astra, 649,474 bbl.; Oriente, 42,237; Ferrocar-rilera, 1,337,380; Comp. Indust. y Comm., 609,092, Solano, 64,158; Diadema, 298,114. b Standard Oil Co. and a few smaller companies, Exploratory drilling has also been conducted around the Comodoro Rivadavia field. The Government is drilling at Vuela del Senguer south of Colonia Sarmiento and about 200 km. west of the main field hut the prospect of success is not as yet large. The country around Castillo, where the Royal Dutch Co. has property, is regarded more favorably. perhaps the most interesting event of the year was the discovery of a productive horizon at Comodoro Rivadavia about 200 m. below that previously exploited. This new horizon was found by the Ferrocarrilera Co. at 769 m. in its well No. 81, the previous yield for this

Jan 1, 1929

By E. H. Griswold

The surveying of oil wells has in recent months become a common practice in the deep fields of the Mid-Continent area. Borehole surveys have been made by mining companies for many years, but the introduction of such methods into the oil fields has been delayed until the past few years, because the value of survey data was not fully appreciated. The acid and gelatin bottle methods of obtaining the angle of deviation and the floating compass method of obtaining the direction of horizontal drift have been in use for more than 20 years. A photographic recording instrument consisting of a plumb bob, magnetic needle and electrically operated camera was devised and used in the Rand mining fields of South Africa prior to 1912.1 Another and improved photographic instrument, depending upon orientation of the drill pipe instead of polar magnetism for direction, has been invented and used. The acid bottle method has also been used in conjunction with oriented drill pipe. The magnetic compass is not reliable for oil-well work because of the unsymmetrical attraction of the needle to the well casing and possible magnetic formations. Many engineers also concur in the opinion that orientation of the drill pipe from instrument to surface will be inaccurate because of the torque exerted between the drill pipe and walls of the hole, causing the lower sections of pipe to twist. When it is considered that 4000 ft. of 6 in. drill pipe has approximately the same slender-ness ratio as 6 ft. of silk thread, such twisting effects can be readily visualized. The gyroscopic compass has been suggested for use in direction finding, but the high cost of such instruments will prohibit their use, except in special cases. Due to the lack of accurate direction-finding instruments, almost all of the survey work in the Mid-Continent fields has been of the acid bottle method alone.

Jan 1, 1929

By E. G. Beinlich

The continuing search for faster, safer, and more economical methods of excavating underground openings has led the staff of the Mather mine of the Negaunee Mine Co. directly to mechanical boring of raises and drifts. The mine is located within the city limits of Negaunee and Ishperning in the eastern portion of the Marquette Iron Range in the Upper Peninsula of Michigan. It is owned jointly by McLouth Steel Corp., Bethlehem Steel Corp., Republic Steel Corp., and The Cleveland-Cliffs Iron Co., who also serves as the operating agent. A total of 2,400,000 tons of iron ore averaging over 60% Fe is mined annually by the block-caving method. This provides feed for the Pioneer pellet plant at Eagle Mills where 1,450,000 tons of pellets are produced yearly with the remaining tonnage being sold as coarse ore. Technical staff of Cleveland-Cliffs have long realized that improved methods of advancing raises and drifts were a necessity if underground mining of iron ore was to survive the transition period in the steel industry's requirements from direct-shipping ore to pelletized ores. For this reason, the Mather mine embarked upon an experimental raise-boring program with a prototype machine in 1961. Improvements since that time in equipment and practice have resulted in the acceptance of mechanical boring of raises as a standard development tool and a vital link in the fulfillment of an orderly development schedule. Advancement of large-diameter openings such as main-level drift headings by mechanical methods in the harder, more competent types of rock has developed more slowly in the mining industry due to the need for more compact and portable machinery and improved bit technology. Many of the obstacles have been overcome by the manufacturers, and in March 1967 it was decided to proceed with a program to bore approximately 4000 ft of 13-ft-diam drift in the Mather graywacke footwall rock.

Jan 1, 1970

SINCE the adoption by the U. S. Bureau of Standards several years ago of specifications for standard 100- and 200-mesh sieves, frequent requests have been received that this Bureau test and certify sieves of other sizes than these. With a view to the adoption of a series of standard testing sieves which might be of use to all industries making fineness tests, this Bureau for .two years has been studying the question of such a standard screen scale. Various scales that have been proposed were considered, and information was sought of representative firms in the various industries interested as to their requirements. Manufacturers of sieves have also been consulted as to the desirability of different screen scales and the practicability of their manufacture. As a result of this study of the question, a conference was called at the Bureau of Standards, Apr. 20, 1916, of representatives of various committees of the American Society for Testing Materials, American Society of Civil Engineers, American Institute of Mining Engineers, American Foundrymen's Association,. [Mining and Metallurgical Society of America, American Water Works Association, American Institute of Metals and the American Spice Trade Association; also representatives of the Committee of Revision of the U. S. Pharmacopoeia, the U. S. Geological Survey, the U. S. Bureau of Mines, the U. S. Office of Public Roads and Rural Engineering, the U. S. Office of Grain Standardization and the U. S. Bureau of Standards; also representatives of a number of private firms engaged in industries in which sieves are used, such as the glass, the drug milling, the abrasive, the asphalt, the mining, the spice, the chemical, and the graphite industries; also representatives of the firms in this country manufacturing wire cloth and sieves. This Conference, after considering the various screen scales either proposed or now in use, adopted as a Standard Screen Scale that given in Table 1, and recommends that it be adopted generally by scientific,

Jan 6, 1917

By J. Weijdema, D. N. Dietz

In the conventional underground combustion process (dry combustion) much heat is left behind in the swept formation and goes to rva.rte. Econonmy can be improved by heat recuperation through water injection. This is most advantageous if done at the earliest opportunity before much heat is dissiputed to cap and base rock. Water injected simultaneously with the air will flash to superheated steam, which passes through the combustion front together with the nitrogen from the air. A condensation front traveling up to three times as fast as the combustion front drives out the oil. In this type of wet combustion, the water evaporates before it reaches the combustion zone. The evaporation front travels more slowly than the combustion zone. If so much water is injected that the evaporation front overrun the combustion front, combustion in that spot will be quenched and some unburned fuel will be left behind. Air reacts with the oil farther down-stream where steam temperatures occur; at steam temperature, the air reacts rapidly with the oil. Velocity of the combustion front is increased thereby and is governed essentially by the water-injection rate. In the extreme case of high water-injection rate, a short heat wave of constant length is driven through the formation by water injection. Once this wave has been established, no more heat need be generated than that required to make up the heat losses from the short heat wave; a relatively low rate of air injection will suffice. The feasibility of partially quenched combustion has been confirmed in tube experiments. A heat wave at steam temperature is observed. Chemical analyses of flue gas indicate preferential burning of hydrogen while a carbonaceous residue is left in the formation. Introduction A disadvantage of so-called dry in situ combustion is that air-compression costs are rather high. An air consumption of about 400 std cu m/cu m (400 scf/cu ft) of formation swept is an accepted figure. This high consumption is mostly wasted since much heat is left behind in the depleted oil sand. Methods were investigated for recuperating as much as possible of the heat left behind. This paper deals only with basic principles and is confined mainly to one-dimen- sional flow without lateral heat losses; experiments were conducted in relatively narrow, well insulated tubes. If some water is injected with the air, it will turn to superheated steam in an evaporation front, which should travel behind the combustion front. The steam having passed the combustion front causes a steam drive by a condensation front that can travel faster than the combustion front. The latter needs to travel only part of the distance covered by the oil-displacing condensation front, and thus consumes less air. The water-air ratio would seem limited to that at which cold water overruns the combustion. This limitation was deliberately exceeded considerably in theory and experiments. It was found that combustion is then indeed quenched, but only locally. Farther downstream, the oxygen finds residual oil at steam temperature, which is suficiently high to ensure rapid oxidation. Thus, the combustion front uses only part of the available fuel because it is chased through the formation faster than its normal velocity. No heat is left behind. This new process is called "partially quenched combustion". At the upper limit of the water-air ratio, a small heat slug is moved through the formation by the flow of water and steam. Only a small flow of air is needed since it has only to generate sufficient heat to make up for the lateral heat losses of the short heat slug. Theory Although many factors complicate underground combustion, the processes will be presented in their simplest form. For this reason, one-dimensional flow without lateral heat losses is assumed. Heat conduction in the direction of flow also is disregarded. Under these conditions, dry combustion causes very high temperatures. The heat-carrying capacity of the gas stream is small. Heat generated by oxidation of a residual oil saturation is retained in the sand. The available fuel determines the air requirement and the temperature obtained. Accepting the often-mentioned air consumption of 400 std cu m/cu m (400 scf/cu ft) formation, we calculate a temperature of the swept sand of 1,200C (2,192F) (Fig, I). If water is injected at a modest rate with the air, it will flash to superheated steam upon contact with the heated sand. One cu m (35.31 cu ft) of hot formation will evaporate about 0.5 cu m (17.66 cu ft) of water, and thereafter will accommodate (at an estimated 0.80 saturation and an assumed 0.40 porosity) another 0.3 cu m (10.59 cu ft) of water in cold condition. As long as less than 0.5 + 0.3 = 0.8 cu m (28.25 cu ft) of water is injected for every 400 std cu m (14,125 scf) of air (water-

Jan 1, 1969

By W. R. Purcell

An apparatus is described whereby capillary pressure curves for porous media may be determined by a technique that involves forcing mercury under pressure into the evacuated pores of solids. The data so obtained are compared with capillary pressure curves determined by the porous diaphragm method, and the advantages of the mercury injection method are stated. Based upon a simplified working hypothesis, an equation is derived to show the relationship of the permeability of a porous medium to its porosity and capillary pressure curve, and experimental data are presented to support its validity. A procedure is outlined whereby an estimate of the permeability of drill cuttings may be made with sufficient acuracy to meet most engineering requirements. INTRODUCTION The nature of capillary pressures and the role they play in reservoir behavior have been lucidly discussed by Lev-rett', Hassler, Brunner, and Deah12, and others. As a result of these publications the value of determining capillary pressure curves for cores has come to be generally recognized within the oil industry. While considerable attention has been directed toward the subject in an effort to provide a reliable method of estimating percentages of connate water, it has been recognized that capillary pressure data may prove of value in other equally important applications. This paper describes a method and procedure for determining capillary pressure curves for porous media wherein mercury is forced under pressure into the evacuated pores of the solids. The pressure-volume relationships ob- tained are reasonably similar to capillary pressure curves determined by the generally accepted porous diaphragm method. The advantages of the method lie in the rapidity with which the experimental data can be obtained and in the fact that small, irregularly shaped samples, e.g., drill cuttings, can be handled in the same manner as larger pieces of regular shape such as cores or permeability plugs. Based upon a simplified working hypothesis, a theoretical equation will be derived which relates the capillary pressure curve to the porosity and permeability of a porous solid, and experimental data will be presented to support its validity. This relationship aplied to capillary pressure data obtained for drill cuttings by the procedure described provides a means for predicting the permeability of drill cuttings. METHODS FOR DETERMINING CAPILLARY PRESSURES Several techniques have so far been employed in determining capillary pressure curves and these fall into two principal categories: (1) Liquid is removed from, or imbibed by, the core through the medium of a high displacement pressure porous diaphragm (2) Liquid is removed from the core which is subjected to high centrifugal forces in a centrifuge4,'. There are? however, certain limitations inherent in both methods. The greatest capillary pressure which can be observed by method (I), above, is determined by the maximum displacement pressure procurable in a permeable diaphragm which at the present time appears to be less than 100 psi. An even more serious limitation of the diaphragm method is imposed hy the fact that several days may be required to reach saturation equilibrium at a given pressure; hence, the time re- quired to obtain a well-defined curve may be measured in terms of weeks. Furthermore, to date, no suitable technique for handling relatively small, irregularly shaped pieces of rock, such as drill cuttings, has been reported and, therefore, measurements must be made, in general, on cores, or portions thereof. The centrifuge method offers the distinct advantage over the porous diaphragm method of arriving at saturation equilibrium in a relatively short time by virtue of the elimination of the transfer medium for the liquid. The calculation of capillary pressures from centrifuge speeds is somewhat tediousa, however, and the equipment required is fairly elaborate. While there exists the possibility that this method might be adaptable to the determination of the capillary pressures of cuttings, this particular ramification has not been investigated, as far as is known. In view of the limitations of the two principal methods for determining capillary pressures, the apparatus described in the following sections has been devised in order that difficulties previously encountered might be circumvented. MERCURY INJECTION METHOD FOR DETERMINING CAPILLARY PRESSURES Theory The methods described above for determining capillary pressures are characterized by the fact that one of the fluids present within the pore spaces of the solid is a liquid which "wets" the solid, i.e., the contact angle which the liquid forms against the solid is less than 90" as measured through that phase. For these "wetting" liquids the action of surface forces is such that the fluid spontaneously fills the voids within the solid. These forces likewise oppose the withdrawal of the fluid from the pores of the solid.

Jan 1, 1949

By W. R. Purcell

An apparatus is described whereby capillary pressure curves for porous media may be determined by a technique that involves forcing mercury under pressure into the evacuated pores of solids. The data so obtained are compared with capillary pressure curves determined by the porous diaphragm method, and the advantages of the mercury injection method are stated. Based upon a simplified working hypothesis, an equation is derived to show the relationship of the permeability of a porous medium to its porosity and capillary pressure curve, and experimental data are presented to support its validity. A procedure is outlined whereby an estimate of the permeability of drill cuttings may be made with sufficient acuracy to meet most engineering requirements. INTRODUCTION The nature of capillary pressures and the role they play in reservoir behavior have been lucidly discussed by Lev-rett', Hassler, Brunner, and Deah12, and others. As a result of these publications the value of determining capillary pressure curves for cores has come to be generally recognized within the oil industry. While considerable attention has been directed toward the subject in an effort to provide a reliable method of estimating percentages of connate water, it has been recognized that capillary pressure data may prove of value in other equally important applications. This paper describes a method and procedure for determining capillary pressure curves for porous media wherein mercury is forced under pressure into the evacuated pores of the solids. The pressure-volume relationships ob- tained are reasonably similar to capillary pressure curves determined by the generally accepted porous diaphragm method. The advantages of the method lie in the rapidity with which the experimental data can be obtained and in the fact that small, irregularly shaped samples, e.g., drill cuttings, can be handled in the same manner as larger pieces of regular shape such as cores or permeability plugs. Based upon a simplified working hypothesis, a theoretical equation will be derived which relates the capillary pressure curve to the porosity and permeability of a porous solid, and experimental data will be presented to support its validity. This relationship aplied to capillary pressure data obtained for drill cuttings by the procedure described provides a means for predicting the permeability of drill cuttings. METHODS FOR DETERMINING CAPILLARY PRESSURES Several techniques have so far been employed in determining capillary pressure curves and these fall into two principal categories: (1) Liquid is removed from, or imbibed by, the core through the medium of a high displacement pressure porous diaphragm (2) Liquid is removed from the core which is subjected to high centrifugal forces in a centrifuge4,'. There are? however, certain limitations inherent in both methods. The greatest capillary pressure which can be observed by method (I), above, is determined by the maximum displacement pressure procurable in a permeable diaphragm which at the present time appears to be less than 100 psi. An even more serious limitation of the diaphragm method is imposed hy the fact that several days may be required to reach saturation equilibrium at a given pressure; hence, the time re- quired to obtain a well-defined curve may be measured in terms of weeks. Furthermore, to date, no suitable technique for handling relatively small, irregularly shaped pieces of rock, such as drill cuttings, has been reported and, therefore, measurements must be made, in general, on cores, or portions thereof. The centrifuge method offers the distinct advantage over the porous diaphragm method of arriving at saturation equilibrium in a relatively short time by virtue of the elimination of the transfer medium for the liquid. The calculation of capillary pressures from centrifuge speeds is somewhat tediousa, however, and the equipment required is fairly elaborate. While there exists the possibility that this method might be adaptable to the determination of the capillary pressures of cuttings, this particular ramification has not been investigated, as far as is known. In view of the limitations of the two principal methods for determining capillary pressures, the apparatus described in the following sections has been devised in order that difficulties previously encountered might be circumvented. MERCURY INJECTION METHOD FOR DETERMINING CAPILLARY PRESSURES Theory The methods described above for determining capillary pressures are characterized by the fact that one of the fluids present within the pore spaces of the solid is a liquid which "wets" the solid, i.e., the contact angle which the liquid forms against the solid is less than 90" as measured through that phase. For these "wetting" liquids the action of surface forces is such that the fluid spontaneously fills the voids within the solid. These forces likewise oppose the withdrawal of the fluid from the pores of the solid.

Jan 1, 1949

By J. H. Swisher

The solubility of sulfur and rate of solution of sulfur in pure Lron were measured in H2S + H2 and H2S + H2 H2O gas mixtures. The solubility and diffusivity of sulfur at 1410°Care 0.13 pet S and 1.0 x 10-5 sq cm per sec, respectively. The solubility iS the same, but the rate of sulfurization is slower in the presence of H2O in the reacting gas. Under these conditions, the over-all rate is controlled jointly by a slow surface reaction and by solid-state diffusion; the mechanism for the surface reaction has not been identified. KNOWLEDGE of the behavior of sulfur in solid iron is desirable for the metallurgy of such products as free machining steel, where a high sulfur level is required, and inclusion-free high-strength steels, where the sulfur specifications are very low. The present investigation was undertaken to check previously reported values for sulfur solubility and diffusivity in 6 iron, and to study the poisoning effect of chemisorbed oxygen on sulfurization kinetics in H2-H2S-H2O gas mixtures. All of the experiments were performed at 1410°C. The thermodynamic behavior of sulfur in 6 iron was the subject of a paper by Rosenqvist and Dunicz.' The sulfur solubility at 1400" and 1500°C was determined by equilibrating pure iron specimens with H2-H2S gas mixtures. The maximum solubility of sulfur in 6 iron was alsc determined by Barloga, Bock, and parlee2 by reacting iron wires with sulfur in sealed capsules. In another investigation, the diffusion coefficient of sulfur in 6 iron at temperatures up to 1450°C was measured by Seibel.3 The method used was to measure sulfur concentration profiles in diffusion couples containing radioactive sulfur EXPERIMENTAL Apparatus. A vertical resistance furnace wound with molybdenum wire and containing a recrystallized alumina reaction rube was used for the experiments. The hot zone in the furnace was approximately 2 in. long with a temperature variation of ±3oC. The hot zone temperature was automatically controlled to within ±2°C, and the test temperature was measured with a pt/Pt-10 pet Rh thermocouple before and after each experiment. Flow rates of the reacting gases were obtained using capillary flow meters. Materials. The source of H2S in the gas train was a premixed cylinder containing 5 pet H2S in H2. This mixture then was diluted with additional hydrogen and argon. In some experiments, water vapor was introduced by passing hydrogen and argon through a column containing 10 pet anhydrous oxalic acid and 90 pet oxalic acid dihydrate. The vapor pressure of water above this mixture is well-known.4 Argon was used as a diluent to minimize thermal segregation of H2S in the furnace5 and to reach higher H2O:H2 ratios than could be obtained in mixtures of H2 and H2S alone. Argon was purified by passage over copper chips at 350°C and subsequently over anhydrone. Hydrogen was purified by passage over platinized asbestos at 450°C and then over anhydrone. The H2-H2S mixture was purified by passage over platinized asbestos and then over P2O5. The specimen stock was made by melting and vacuum-carbon deoxidizing electrolytic "Plastiron" in a zirconia crucible. The principal impurities are listed in Table I. In some of the equilibrium experiments, six-pass zone-refined iron was used to minimize impurity side effects. This zone-refined iron had a total impurity level of about 25 ppm. Procedure. Specimens were annealed in hydrogen for a period of at least 2 hr at the beginning of each experiment. The specimens were held in the reacting gas for times varying between 10 min and 17 hr, and cooled to room temperature in a water-cooled stainless-steel block at the bottom of the furnace. The pH2S/pH2 ratios reported are those for gas equilibrium at 1410°C. Calculations based on available thermodynamic data8 showed that the only other gaseous8 species that formed in significant amounts in the furnace were S2 and S. Even when water vapor was introduced into the gas mixture, the concentrations of SO2, SO, and so forth, were negligible. The initial partial pressure of H2S was therefore corrected for its partial dissociation to S2 and S in determining the equi-

Jan 1, 1968

By Lewis E. Dr. Young

MINING engineers in the United States understand that mining conditions in the British coalfields are much more difficult than in most of the mines now being operated in the United States. We realize also that in the near future we must face some of these same difficult problems. Early Mechanization The progress made in mechanical loading in the United States is the result of a long struggle in many coalfields to mine with power tools safely and to increase output per man-shift. Attempts to use power to loosen coal and to transport broken coal in the U. S. may be said to date from the Stanly Header, or Entry-Driver brought from England in 1888. The principle of this boring machine was used in the McKinlay Entry-Driver, almost continuously used in the U. S. since 1920. Since 1888 experimental loaders, scrapers, and conveyors were installed with more or less success. Beginning in 1918, considerable progress was made with mobile loaders, and in 1920 the first wage agreement for the operation of mechanical loaders was made in Indiana. In 1923 the Pocahontas Fuel Co. loaded nearly 1 million tons of coal using 23 Coloders. Labor Policy The United Mine Workers of America have never officially opposed the Mechanization movement. On December 10, 1945, in a statement before the House of Representatives Labor Committee, John L. Lewis said, regarding the policy of the United Mine Workers of America: "We have welcomed progress; we have welcomed machines. We have told our people that they had to accept that condition; that it was the process of progress, and that they would have to take their chances." Recent Development In 1951 about 71 pct of the tonnage mined underground was mechanically loaded. Over 4000 shuttle cars are in service and it is estimated that much more than half of the tonnage loaded underground is produced by trackless mining. In 1947 roof-bolting was introduced extensively and it is estimated that more than 2 ½ million bolts are now being used per month in about 600 mines. The use of roof bolts has permitted the more effective and safer use of loaders and shuttle-cars. Continuous Mining The McKinlay Entry-Driver could have been used for continuous mining, but for many years it was used only .for entry driving. In 1946 the Silver machine was developed in Colorado, and in 1947 this was acquired by the Joy Mfg. Co. and called the Joy Continuous Miner. Other types of combination mining-loading machines which eliminate drilling and blasting operations are the Marietta Miner, the Colmol, the Lee-Norse Miner, the Junior Miner, the Goodman and the Konnerth machines. There are several other types in the process of development. Probably by January 1953 there will be about 250 continuous miners in operation in the U. S. Payment of Mine Labor One of the most important problems in mechanizing was the establishing of rates of pay that would be attractive to the best men. Prior to the installation of mobile loaders the hand loaders and cutters have been paid by the ton. It was felt that a system of a day's pay should be established and that piece and tonnage rates should be abolished completely. Without exception, all coal loaded in mines equipped with mobile loaders is prepared and loaded by men paid an hourly rate. Trends in Mining Research There are two diverse approaches in coal production research; to try to design a mining machine to fit current methods, or to adapt mining practice to take advantage of proven machines. A great deal of credit must go to the mine operators who have been enterprising and dynamic enough to use available equipment intensively and to discard it as soon as an improved or new machine is available. Effect of Changing Markets Formerly there was an important demand for lump and prepared coal in the larger sizes for domestic use. The use of bituminous coal for house heating has decreased so that not more than 19 pct of the annual tonnage goes to retail trade, only 12 pct is used by the railroads, and much of the retail and most of the railroad coal is in stoker size. As a result of this decline in the market for coarse coal most of the large mining operations have crushers installed in the tipples or preparation plants. Mass production at the face requires increased preparation facilities. Another important trend is in connection with complete seam mining with mechanical loading. In many mines where the immediate roof is apt to fall with the coal no effort is made to separate roof material from coal prior to

Jan 1, 1952

By P. L. Allsman

Butte mining district contains extensive manganese vein deposits forming a peripheral zone. Oxidation in the veins studied usually extends to a depth of about 75 ft. Secondary minerals formed by oxidation were found to be ramsdellite—always accompanied by intermixed pyrolusite—and cryptomelane. Enrichment of the gossan is accomplished by reduction of weight upon oxidation; theoretical enrichment is 32.2 pct. Additional enrichment is caused by leaching of soluble minerals, particularly calcium and magnesium carbonates. BUTTE mining district contains extensive manganese vein deposits in the outer zone, surrounding the copper and zinc deposits and corresponding to the well known silver zone. This article describes the mineralogy of the manganese veins, the oxidation and enrichment processes, and the use of this information in prospecting. Information was derived from a study of the Emma, Star West, Tzarena, and Norwich mines, selected as representative of the district. Vein exposures at these mines were mapped, studied, and sampled on the outcrops and throughout the oxidized zone. Specimens were cut and polished for minera-graphic examination, identification, and textural studies. Knowledge of the manganese oxide minerals is scanty, previous information having been rendered obsolete by publication of the first correctly identified list of manganese oxide minerals by Fleischer and Richmond in 1943. Positive identification of the manganese oxides is possible only by X-ray analysis. Identifications for this study were made by the author with a Phillip's Diffractometer at the Montana School of Mines and confirmed by Lester Zeihen of The Anaconda Co., using a Norelco X-ray camera. It was necessiary to re-evaluate some X-ray data, as published patterns of several manganese oxides proved to be of mixtures, mostly showing pyrolusite as a contaminant. Perhaps the most useful information on oxidation and enrichment of manganese is presented in recent books by Goldschmidt1 and Rankama and Sahama.2 While their hypotheses are not conclusively proved, all laboratory and field evidence has served to substantiate them. This information was very useful in this study. Mineralogy: The primary minerals of the manganese veins are chiefly rhodochrosite and quartz. Rhodonite is abundant in the northern part of the district and in places has been found to comprise over a third of the vein matter. A variable but generally small amount of sulfides may be present, principally pyrite and silver minerals. Sphalerite is progressively more abundant near the zinc zone. Rhodochrosite is believed to form complete iso-morphous series with siderite, ankerite, and calcite. Some variation into these compositions is common, and the intermediate forms are termed manganosid-erite, manganankerite, and rnanganocalcite. Much of the rhodochrosite is remarkably pure. Other manganese minerals in the district include huebner-ite, alabandite, and helvite. Ramsdellite (MnO2, orthorhnmbic) is the principal manganese oxide mineral, comprising perhaps two-thirds of the total oxides. It is dull to iron black, and generally massive or platy in structure. A prominent platy cleavage is the only distinguishing megascopic characteristic. Pyrolusite (MnO2, tetragonal) is next most abundant to ramsdellite, with which it is usually intimately mixed. The luster is often brighter or more metallic than in ramsdellite, and needle-like crystals are diagnostic. Pyrolusite is common in small cavities formed by oxidation of pyrite grains. It is relatively abundant in zones of high limonite content. Cryptomelane (KMnO16 tetragonal ?) is rare in the outcrop, but becomes more abundant with depth. At depths of several hundred feet it is the principal oxide. Although its appearance varies, a blue-black flinty luster and blocky to conchoidal fracture are most common. A potassium flame test will identify this mineral. Hardness of all three oxides varies from 2 to 6. The three are quite commonly intermixed, and their textures can vary greatly. The commonest textures are massive or colloform, representative of colloidal deposition, or vuggy and boxwork textures, formed by partial leaching and oxidation in place. A box-work of either ramsdellite or chalcedony is formed after rhodochrosite rhombs and is indicative of ore shoots in this district. Some replacement of both quartz and the granitic wallrock by ramsdellite has been noted, but most of the oxide was deposited as a fissure filling by fine particles. No trace of manganite, hausmannite, braunite, or manganosite was found. No minerals of the psilome-lane group were detected besides cryptomelane. Amorphous MnO, was found at several spots. A specimen of oxide coated with yellow barite crystals was amorphous and not psilomelane (BaMn9O18. 2H2O). Voids formed by the leaching of sphalerite were coated with cryptomelane, not hetaerolite (ZnMn2O4) as might be expected. No manganese sulfate minerals were found in the gossans; however manganese alum (apjohnite ?) has been re-

Jan 1, 1957

By H. R. Barnhurst

It would be a difficult matter to trace from the beginning the very few improvements made in the burning of fuels prior to 1860. Donbtless the crossing of the sticks of wood in building a mood fire early appealed to our savage ancestry as a means of expediting its effectiveness for their crude culinary purposes. Stones and andirons came later in assisting the admission of air to the under part of the fuel bed, while beacons and cressets, utilized metal bars as supports for the same purpose. It is probable that Tuba1 Cain owed his success to the use of bellows making possible the use of mixed fuel and charge upon a hearth. With the development of working in cast iron, grate bars came in, and they are still with us doing duty in every household and almost every art where heat is a factor. Little was done beyond these crude methods prior to 1860. With the advancement of knowledge came the fuel-gas producer, a natural child of the retorts employed in supplying illuminating gas. It is only within the last 15 years that the conclusion became general that complicated systems for saving heat would not remedy deli-. ciencies in its primary development, and within that time there has been great advancement in the means of producing initially a fire of high effciency, so that to-day we are moving rapidly toward both high development and high absorption, with the resultant of high efficiencies. In studying the subject of the availability of pulverized coal as a fuel, it may occur to ask, why has this not come up earlier? This, question would be naturally prompted by recalling the fact that Thomas Crompton's English patents upon his methods were issued to him nearly 40 years ago. A conclusive answer to this, however, is that Crompton at that time had very crude facilities for making what was at best a very imperfect pulverization of the coal, arid the expense of preparation mas very great. He does not seem to have been aware of the advantage of a thorough drying of the coal in the

Jan 1, 1914

By F. D. Rosi

IN the production of single crystals by the Bridg-man method of solidification from the melt in vacuum at a crucible lowering rate of 0.25 in. per hr, a cellular structure was frequently observed in copper and copper-base alloys at the terminal surface of the as-cast crystals (i.e., the surface representing the last portion of the crystal to solidify). The geometrical form of this structure varied from crystal to crystal, but, in general, could be classified as either hexagonal or quadrilateral. Fig. 1 shows examples of this cellular structure, which is similar to that reported by Buergerl and, more recently, by Pond and Kessler&apos; and Rutter and Chalmers. In the micrographs of Figs. lb and c, the cubic structure in the alloy crystals is obscured somewhat by excessive surface evaporation in the final stages of solidification. X-ray orientation studies indicate that the traces outlining the various geometrical forms correspond to octahedral planes, which are the planes of greatest reticular density in the face-centered cubic lattice. It would appear from this that the view first propounded by Bravais,4 that the surface energies and normal growth velocities of the different crystal planes are inversely proportional to their reticular densities, applies to this cellular structure, since those surviving are the planes of greatest atomic density. Thus, the observed variation in the geometrical form of this structure in crystals of different orientation is readily understandable from the distribution of the (111) planes in the standard {111}, (1101, and (1001 stereographic projections. Depending upon whether the crystal axis (i.e., the direction of crystallization) coincides with a <111>, <111>, or <100> direction, the cellular structure viewed from a surface perpendicular to the crystal axis will consist of a network of regular hexagons, skewed hexagons (with interfacial angles of 110" and 125"), or cubes, respectively. It follows, moreover, that off-orientations from these principal directions will yield modifications of these three basic geometric configurations. In this connection, it is interesting to note that the bounding planes of the hexagonal structure observed in tin by Rutter and Chalmers3 showed no preferred orientation.

Jan 1, 1954

By R. Maddin, S. K. Tung

SUCCESS of the dislocation theory in formulating the transitional lattice theory proposed by Har-greaves and Hill in 1929&apos; is well established for low angle grain boundaries. The theoretical work of Burgersa and Read and Shockley,3 together with the experimental observations of Aust and Chalmers4 and Parker and colleagues,6 leaves little doubt as to the structure of grain boundaries with differences of orientations up to between 15" and 20". Beyond these angles, the structure of the boundary is not so clear, and is still a matter for conjecture. There have been notable experiments devised from which the data could be used to calculate energetics for possible arrangements of atoms in forming a large angle boundary.6 Most of these experiments deal with diffusion through and along the grain boundary. The recent work of Rhines and Cochart7 and Rhines, Bond, and Kissel18 was concerned with the relative movement of grains in aluminum bicrystals under constant tensile loads with their boundaries aligned at 45 " to the tension axis. The gliding along the grain boundary was cyclic and began after an incubation period. The velocity of gliding increased with the sum of the angular difference, 8, between the operative slip direction in the conjugate crystals and the angular difference between the active slip planes as measured between their traces upon the grain boundary. The initial gliding rate varied with temperature, and the logarithm of the average gliding taken over a considerable period was a linear function of the reciprocal of the absolute temperature: the slope gave an activation energy of 11,000 ±1,000 cal per mole. Since the rate of grain boundary shear is sensitive to the misorientation of the grains themselves, as shown by several workers,7,8 it is suggested that further work of this type might be fruitful in adding information regarding the behavior of boundaries under stress. The techniques devised by Chalmers" added impetus to the facility for observing grain boundary behavior, in that they provided a simple means for producing bicrystals of predetermined orientation so that the angle of the boundary could be controlled,

Jan 1, 1958

By F. Keller, E. H. Dix

The desirable high strength and hardness of the heat-treated strong aluminum alloys result from two distinct structural changes: (1) the formation of a solid, solution by heating at the required temperature for a sufficient period, and the substantial retention of this solid solution by rapidly quenching; (2) precipitation of particles of constituent and coalescence to a critical size to produce maximum strength and hardness. In alloys of the duralumin type, that is, alloys containing both copper and magnesium silicide precipitation takes place at normal atmospheric temperature, whereas in alloys containing copper without magnesium silicide or magnesium silicide without copper, maximum properties are obtained only after an accelerated aging treatment consisting of heating for 15 to 20 hr. at temperatures of about 150" C. The mechanical properties of these alloys subsequent to quenching but prior to aging are ideal for forming operations. Unfortunately, however, the alloys of the duralumin type age very rapidly during the first 24 hr. and aging is substantially complete after four days. For severe forming, such as the heading of rivets, it is desirable that this be accomplished within ½ hr. or at the most 2 hr. after quenching. Alloys containing magnesium silicide without copper also age at normal temperatures but the aging is less rapid and the material can be satisfactorily worked within several weeks after quenching. Some slight aging of alloys containing copper alone also takes place at room temperature but it is unimportant from the standpoint of workability. Any method of retarding the aging at room temperature of the duralumin type of alloys would be of considerable advantage in that the period during which the material could be worked successfully would be lengthened. For instance, in aircraft plants it is customary to supply the workmen with small lots of rivets that should be used within ½ hr . after heat treatment. Such procedure has the obvious disadvantage of being uneconomical, and furthermore there is always the possibility that the workmen would use the rivets after the time limit had expired, or the supply being depleted might use some that had not been heat-

Jan 1, 1931

By G. R. Brophy, A. J. Miller

The Grossmann principle1 for the calculation of hardenability of steel from composition is attractive because of its simplicity. It postulates that the hardenability of a steel for any particular grain size may be expressed in terms of an ideal critical diameter, which is the product of an ideal critical diameter for a "pure" iron-carbon base multiplied by a succession of factors for each element of composition contained, including the incidentals. It infers that the multiplying factor for a given quantity of an element is constant for all combinations of composition. Gross-mann has stated that in the great majority of cases the experimental values of hardenability are found to be well within 10 per cent of the calculated values. The validity of the scheme has been confirmed in principle by Crafts and Lamont2,3 and by Kramer et al.4 Their results differ from the original in the magnitude of the effect of some elements but, since they accepted the product concept and followed its direction, it is to be ex~ected that similar results would be obtained. Crafts and Lamont, in their second Paper, recognized that the factor relations for manganese and nickel were not continuously linear, but beyond certain critical amounts increase sharply. Austin, Van Note and Prater6 demonstrated nonlinear relations between hardenability and alloy contents. Their curves for chromium, silicon, manganese and nickel were all convex upward to show decreasing incremental effects. They concluded that Grossmann&apos;s factors under-evaluate the hardening effect of low percentage additions of these elements, and overevaluate the larger additions. More recently W. Stevens has found that the factor method fails when applied to complex steels containing two or three principal alloying elements other than carbon. Multiplying factors derived from his results bear a complex relation to composition and are not constant for a given amount of an element as the base composition varies. C. A. Liedholm7 found that, using either the Grossmann or the Crafts-Lamont multiplying factor values, not only were the relative hardenabilities of two heats of S.A.E. 6130 chromium-vanadium steel

Jan 1, 1947

By A. J. Miller, G. R. Brophy

The Grossmann principle1 for the calculation of hardenability of steel from composition is attractive because of its simplicity. It postulates that the hardenability of a steel for any particular grain size may be expressed in terms of an ideal critical diameter, which is the product of an ideal critical diameter for a "pure" iron-carbon base multiplied by a succession of factors for each element of composition contained, including the incidentals. It infers that the multiplying factor for a given quantity of an element is constant for all combinations of composition. Gross-mann has stated that in the great majority of cases the experimental values of hardenability are found to be well within 10 per cent of the calculated values. The validity of the scheme has been confirmed in principle by Crafts and Lamont2,3 and by Kramer et al.4 Their results differ from the original in the magnitude of the effect of some elements but, since they accepted the product concept and followed its direction, it is to be ex~ected that similar results would be obtained. Crafts and Lamont, in their second Paper, recognized that the factor relations for manganese and nickel were not continuously linear, but beyond certain critical amounts increase sharply. Austin, Van Note and Prater6 demonstrated nonlinear relations between hardenability and alloy contents. Their curves for chromium, silicon, manganese and nickel were all convex upward to show decreasing incremental effects. They concluded that Grossmann&apos;s factors under-evaluate the hardening effect of low percentage additions of these elements, and overevaluate the larger additions. More recently W. Stevens has found that the factor method fails when applied to complex steels containing two or three principal alloying elements other than carbon. Multiplying factors derived from his results bear a complex relation to composition and are not constant for a given amount of an element as the base composition varies. C. A. Liedholm7 found that, using either the Grossmann or the Crafts-Lamont multiplying factor values, not only were the relative hardenabilities of two heats of S.A.E. 6130 chromium-vanadium steel

Jan 1, 1947

By W. J. Hillenbrand

The soda-ash method for eliminating arsenic from a molten copper bath has been described previously in some detail.&apos; Briefly, the process consists in blowing powdered sodium carbonate under the surface of the partially oxidized melt and in removing the slag formed, which will contain a certain proportion of the arsenic formerly in the bath. Sodium carbonate melts readily at the temperature of molten copper, and when molten it dissolves arsenic oxide rather rapidly. In the process, sodium arsenate is formed which is removed along with the excess of molten soda ash. In order that arsenic may be eliminated in this way, it must first be oxidized to the pentavalent condition. This, however, is easily accomplished by blowing air into the molten copper until a fair excess of cuprous oxide is present. The manner in which soda ash is introduced into the furnace has a considerable effect upon the efficiency of the process. In the earliest attempts at arsenic removal, soda ash—often in combination with slaked lime, for sodium carbonate is not the only solvent that will remove arsenic—was thrown upon the surface of the bath, was allowed to melt, and was removed after it had dissolved a sufficient amount of arsenic. At present powdered soda ash is generally blown in under the surface of the melt with the aid of compressed air. Melting immediately as it comes into contact with the molten copper, it can react with considerably more of the bath than by the former method, and thus can remove arsenic more rapidly and more completely. Since the resulting slag is removed at once, its very destructive effect upon the furnace refractories is minimized. The effectiveness of the soda-ash method may be gathered from the results of the following test. A 900-lb. charge of copper was melted in a small, oil-fired reverberatory furnace, and sufficient metallic arsenic was added to the bath to bring the concentration of that element to about 0.5 per cent. Air was blown into the melt until its oxygen content was just under 1 per cent by weight. The bath was then sampled and soda ash was blown in under the surface in 5-lb. batches. After each addition

Jan 1, 1934

By Frederick N. Rhines

Pure copper that has been allowed to oxidize at an elevated temperature in the air is found to be covered with two distinguishable layers of oxide scale. The outer of these, which is very thin, is composed of cuprie oxide, while the inner layer, comprising the bulk of the scale, is made up chiefly of cuprous oxide (Fig, la). If a small quantity of an alloying element, such as silicon, is present in the copper, silica particles are found disseminated through the cuprous oxide, deposited most abundantly near the metal surface, and, in addition, silica particles occur to a limited depth within the copper itself (Fig. 1b). It is this inner layer, composetl of oxide particles precipitated in a matrix of metallic copper, that is known as the "subscale" or the zone of internal oxidation. Under a low oxygen pressure it is possible to produce the subscale without the formation of external layers of copper oxides, thus leaving the metal surface bright and apparently clean while oxidation has occurred, in fact, to a considerable depth within the metal (Fig. 2). Although little is yet known in a detailed way of the mechanism of internal oxidation, the general nature of the process is evident. By virtue of the considerable solubility of oxygen in copper,&apos; it is possible to bring the alloying element in contact with oxygen within the metallic solid solution. If the oxide of the alloying element is more stable than cuprous oxide, the foreign oxide may form and, since most oxides are relatively insoluble in copper, it will not long remain in solution, but mill separate as a precipitate. As the metallic solute is exhausted in the zone of precipitation, oxygen that is constantly being supplied at the surface diffuses farther into the alloy and thus produces an ever-thickening shell of subscale. The distribution of the reacting elements in the subscale and adjoining zones must be somewhat as indicated in Fig. 3. The conditions requisite to internal oxidation to be anticipated are thus: (I) a solubility of oxygen in the alloy, (2) the ability of oxygen to diffuse at an appreciable rate into the alloy, (3) the possibility of the

Jan 1, 1940

By Frederick N. Rhines

Pure copper that has been allowed to oxidize at an elevated temperature in the air is found to be covered with two distinguishable layers of oxide scale. The outer of these, which is very thin, is composed of cuprie oxide, while the inner layer, comprising the bulk of the scale, is made up chiefly of cuprous oxide (Fig, la). If a small quantity of an alloying element, such as silicon, is present in the copper, silica particles are found disseminated through the cuprous oxide, deposited most abundantly near the metal surface, and, in addition, silica particles occur to a limited depth within the copper itself (Fig. 1b). It is this inner layer, composetl of oxide particles precipitated in a matrix of metallic copper, that is known as the "subscale" or the zone of internal oxidation. Under a low oxygen pressure it is possible to produce the subscale without the formation of external layers of copper oxides, thus leaving the metal surface bright and apparently clean while oxidation has occurred, in fact, to a considerable depth within the metal (Fig. 2). Although little is yet known in a detailed way of the mechanism of internal oxidation, the general nature of the process is evident. By virtue of the considerable solubility of oxygen in copper,&apos; it is possible to bring the alloying element in contact with oxygen within the metallic solid solution. If the oxide of the alloying element is more stable than cuprous oxide, the foreign oxide may form and, since most oxides are relatively insoluble in copper, it will not long remain in solution, but mill separate as a precipitate. As the metallic solute is exhausted in the zone of precipitation, oxygen that is constantly being supplied at the surface diffuses farther into the alloy and thus produces an ever-thickening shell of subscale. The distribution of the reacting elements in the subscale and adjoining zones must be somewhat as indicated in Fig. 3. The conditions requisite to internal oxidation to be anticipated are thus: (I) a solubility of oxygen in the alloy, (2) the ability of oxygen to diffuse at an appreciable rate into the alloy, (3) the possibility of the

Jan 1, 1940

IN the decade beginning 1850, the development by William Kelly in I the U.S.A. and Henry Bessemer in England of the pneumatic method of refining pig iron, known as the Bessemer process, gave the world the first method of producing low-cost steel in large volumes. Briefly, the Bessemer process consists of blowing air through liquid blast furnace iron in a refractory-lined vessel known as a converter. The air enters the iron in the furnace bottom through tuyeres, and during its passage through the iron removes the carbon, manganese, and silicon by oxidation. The heat produced by oxidation is sufficient to raise the temperature of the liquid metal to normal steel casting temperatures and, in addition, to melt some scrap. In the 1860&apos;s, the open hearth process was introduced which in the early part of the twentieth century surpassed the Bessemer process in steel production. In the early 1870&apos;s, Thomas and Gilchrist discovered that phosphorus could also be removed if lime were added and the converter lined with basic refractory; the modification is known as the basic Bessemer process and is used in Europe. Bessemer steel usually contains between 0.010 and 0.020 per cent nitrogen and between 0.05 and 0.10 per cent phosphorus which influences the properties. Henry Bessemer,1 in 1856, recognized the possibility of using oxygen in the converter process, but the cost was prohibitive. This interest was associated with the theoretical balance of the Bessemer process. Experimental work&apos; has indicated that bottom blowing with pure oxygen results in serious converter bottom and tuyere erosion. Dilution of the oxygen by steam has been observed to be an effective means of maintaining low-nitrogen content of the steel and at the same time reducing bottom and tuyere erosion. A further advantage is that the fume emission characteristic of Bessmer operation is reduced. The addition of steam to the oxygen, however, reduces scrap-melting capacity due to the endothermic reaction characteristics of steam. The possible advantages of refining methods for steel using high-purity oxygen have been recognized for over a hundred years, but the develop-

Jan 1, 1964